Ethers of allyl-type alcohols with



Patented Aug. 26, 1952 UNITED STATES PATENT OFFICE E'TnEns F A LLYL-TYPE ALCOHOLSQ WITH HALOGEN -.CONTAINING SUBSTITUTED CARBINOLS, AND rRocEss Seaver A. Ballard, Orinda, Rupert 0. Morris, Berkeleyya'nd Jolin L. Van Winkle, San Lorenzo, Calif., assignors to Shell Development Comany, San Francisco, Calif., a corporation of Delaware No Drawing.

12 Claims. (01. sin er-4') This invention relates to organic chemical compounds and to a process for the preparation of organic chemical compounds.

More particularly, the present invention relates to a new and unexpected reaction of allyl-type hydrocarbon halides with organic epoxide compounds whereby there are produced valuable unsaturated 'eth'ers "of allyl-type alcohols with aioge -contaimhg substituted carbi'nols that are us'fulin a wide variety of applications, to process for accomplishing the reaction, and to novel and useful products prepared thereby.

The allyl-type hydrc'aca'rbon halides which are reacted with organic epoxide compounds according to the present invention are the olefinic hydrocarbonhalides wherein an atom of halogen iscirecoy linked to a saturated carbon atom and said atom-of halogen is in the allyl position with ijeshe'ctto an olefinic carbon-to-carbon bond; Said halo enatom thusis directly attached to a saturated carbon atom which is directly linked Via a univ'alent bond to a second carbon atom which turn is directly linked Via an olefinic, or aliphatic carbon-'to carbon double bond to a third carbon atom. The'allyl-ltyp'e hydrocarbon halides may also be referred 'to as the beta,gaminaolefihic halides, since they contain an olefinic bond in the betagamma position relative to the manor halogen, and in a morehmited case they may defined as the 2-a1keny1 halides. Although the alkenyl group generally will bean open-chain "a kenm group,- in other cases it may be a cl'osed chain 'alkenyl group, e; g'., a cy l l am yigr'cup.

. 'allfl-type hydrocarbon; halides form a dis= tinctive class of reactive unsaturated compounds which undrg'oreactions that clearly distinguish them froin halogen-substituted hydrocarbons that do hotcontain a halogen atom inthe allyl position relative to an-olefinicbond. Unlike,"for

.p-le, the saturated or the aromatic hydrohalides may .be' polymerized readily to high molecular weight polymers. They "are further distinguished by virtue-of their unique chemical characteristics *from other hydrocarbon halides, such as, for instance, the a1ky1 halidesfthearyl halides, and the aralkyl halides; e. g., by their tendency to rem iihe I-ic products of condensatioma tendency that is hone; in the alkyl halides, the a ryi lialidfs and the aralkyl halides.

Jar-type {hydrocarbon handles have furt er dis me we properties not round in the hydroha d many cas s they react oh halides, the allyl-type hydrocarbon a manner that could not be foretold on the hosts;

ofl reactionsorotherhydrocarhon halides: I

Insofar as 'We are awar the only attempt heretofore to react allyl type hydrocarbon" halides. withbrganic epoxy, compoundse, g2;

alkylene oxides and substituted alkylenejoiiide's'; was by Lopatkin (Journal fur Praktische Chei'nle; [2] 30, 390 (1884)), who by reacting al1yl=iodide and epichlorhydrin in the presence-of-zinc at sponding to one of the probable formulas Insofar as We are aware, the product thus pared has been of only laboratory; or "theoretical interest and has not been found to possess b erties which would make it of commercial value or its production on a large scale oi. interest to the chemical industry.

It now has been surprisingly discovered in accordance with the present invention that valuable products having a high degree of commercial utility may be prepared by reacting allyl-type hydrocarbon halides with organic epoxide compounds by heating under conditionsmore fully described hereinafter, at an-elevated temperature-of from about C. to about 350 C. and in liquidphase, a mixture comprising the allyl-type hydrocarbon halide and the organic epoxidecompound. The products which are produced: in accordance with the process of the present invem tion are very different, from the aforementioned product produced by the above know-nprocess.

Instead of alcohols, the products produced in by heating allyl chloride with epichlcrhyann as hereinafter described there is produced in excellent yields the valuablegther allyl bis(chloromethyDcarbinyl ether. This compound is of wide value in the commercial arts.

resins as hereinafter described, and it has' awide It may be r employed in" the preparation of i new and improved variety of other and important'potential applications. In contrast to the above known reaction of allyl iodide with epichlorhydrin, the new reaction which forms the principle of the present invention enables the preparation of useful and valuable new organic compounds. The reaction, which is readily distinguishable from previous reactions known to us of allyl-type hydrocarbon halides with epoxide compounds, proceeds substantially as illustrated by the specific equation:

It will be seen from the equation that allyl chloride, when caused to react with epichlorhydrin according to the process of the invention combines with the latter as illustrated to produce the valuable unsaturated halogen-containing ether allyl bis(chloromethyl)carbinyl ether. Methallyl chloride and epibromohydrin, when caused to react according to the process of the invention, combine substantially as illustrated in the following equation:

In this reaction, the illustrated product is the valuable compound methallyl ehloro-methylbromomethylcarbinyl ether.

' A still further illustration of the reaction accomplished by the process of the invention is as follows: 1

It will be observed that in the illustrated reaction-,-the ether linkage is at the beta carbon atom f the halogen-substituted hydrocarbon residue; That is, others of allyl-type alcohols with non-primary, i. e., with secondary and with tertiary halogen-substituted alcohols are produced.- This was indeed a surprising result of the process. Various alcohols when suitably re- 7 acted with epoxide compounds containing a I O eer -tthe process afiords an effective method for preparing new and useful others, many of which 4 a could heretofore have been prepared only at considerably greater difficulty and expense,.if at all. I

In accordance with the generic aspects of the invention, the process of the invention may be applied to reacting any allyl-type hydrocarbon halide with any organic epoxide compound containing a'l,2- or 1,3-epoxide ring to produce ethers of allyl-type alcohols with halogen-substituted alcohols. The generic equation expressing the reaction as thus broadly applied is substantially as follows:

l l I I In this equation, X represents an atom of halogen, preferably bromine or chlorine; the formula represents the allyl-type hydrocarbon halide; the formula o represents the organic epoxide compound; and the unsaturated halogen-containing ether produced as the product of the process is represented by the formula I l C=CC-O-C I It Representative compounds which contain 1,2- and/or 1,3-epoxide rings and with which allyltype hydrocarbon halides may be reacted by heating in liquid phase according to the process of the invention include the alkylene oxides, such as ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, isobutylene oxide, 1,3 epoxybutane, butadiene monoxide, butadiene dioxide, styrene oxide, cyclopentene oxide, 1-3- epoxycyclopentane, as well as substituted alkylene oxides which contain one or more various substituent atoms or groups. Representative substituted epoxide compounds include, among others, epoxide others, such as glycidyl methyl ether, glycidyl ethyl ether, glycidyl propyl ether, beta-ethylglycidyl isopropyl ether, glycidyl neo-. pentyl ether, glycidyl naphthyl ether; nitro epoxides, such as 3-nitro-1,2-epoxypropane, 3-nitro- 2-ethyl-1,2-epoxybutane, and nitrostyrene oxide; epoxide esters, such as methyl 2,3-epoxypropionate, glycidyl acetate, beta-methylglycidyl isobutyrate, and glycidyl naphthenate; and sulfur containing epoxide compounds, such as glycidyl ethyl thioether and alpha-methylglycidyl cyclohexyl thioether.

It has been further discovered according to the invention that allyl-type hydrocarbon "halides may be reacted according to the process of the invention even with epoxide compounds containing a reactive group or atom in addition to the epoxide ring, particularly epoxid-e compounds containing a reactive halogen atom, such as the epihalohydrins and the substituted epihalohyvdrins, to produce, for example, valuable allyltype ethers of dihalogen-substituted secondary and tertiary carbinols. Representative epihalohydrins which maybe employed in the process of the invention include, for example, epichlorohydrin, epibromohydrin, beta-methylepichlorohydrin, alnhaalpha dimethyl pibromohydrin, beta-methylepibromohydrin, beta-ethylepibromohydrin; :cyolohexylepichlorohydrin; .phenyle'pki chloroh'ydrin; and; iabromoe3A-epoxybutane; It is not :always; necessary? that .the'whalogen'awm in: the epihalohydrinsbenlinked ;to a vcarb on atom which fin .turn :is directly .linkedpto a. carbon atom.

of the; epoxy a group; :since allylrtype :hydrocarbonhalides maybe successfully reacted withepihaio hydrins wherein th'ecarbon atom to which the halogenoatom is attached tis one. :or more, times removed from the repoxide ygroup; 1 Furthermore, the: procetsxis anotf limitedi' toi :epihalohydrins con-. taining 1 ,2 ep oxide 3 groups, .since-sallyktype hydrocarbon halidessinay berire'acted accordinggto the 'processrofuthe invention with repihalohydrins.

containing 1,3-epoxide groups asmell; M

LWhile various epoxid'e: compounds mayuberemployed 'inathe processlofith'e invention, apreierred subgroup of. epoxide" compounds which i may be employediin accordance withthe. invention is composed of epihalohydrins wherein the: epoxide group is a ljzepox'ide group containing :in the epoxide ring a GH2- group and havingia halogen-substituted methyl' group directly linked to the other carbonatom' of the epoxide ring, i...e., the glycerolepihalohydrin's. The preferred epoxide compounds may be'represented by the formula J J'-X'+ ohr c ong-x I I R CIHQX -o'=o#-o--o-o--n The productxthus. iormed will be seen to contain a greaternumberofhalogematoms than does either offtheereactants. and,. furthermore, :to con:- tain the halogen atoms in the activated positions characterized by. attachment .toia carbon atom which' in turn: is directly bondedflto a non-primary (i.i=e.,.a secondaryor-tertiary carbon atom. Theliiahyieldspt these distinctive products, and absence of Lapprecl ablenfurther .condensation oi. these products-with either of the: reactants or with theinselves not only were: unexpected results obtained according. touth'e process of. the ,inven-. tion; but suclrresults-proflde good'eviden'ce of the critical. difference; .insofaras theprocess of the inventionz..is concerned, between. hydrocarbon halidesxin which. the-halogen atomniswin. the allyl position relative to an olefinic bond and hydrocarbon halides which do not containa halogen atom the ally l position relative to an olefinic bond. l

The invention inits broad concepts is regarded as .rbieln'g generic. to; reacting. by heating in liquid.

phase as hereinbefore. and hereinafter. described anyibetagammamlefinic hydrocarbonhalide with organic epoxide compounds containing;1,'2.-

1 and/or 1,3-epoxide rings to produce ethers of betagamma-olefinic alcohols with halogen-substituted non-primary alcohols. In the allyl-type hydrocarbon halide, the saturated carbonatom to which the halogen atom is. directly linkedmay be" a. primary "carbon atom (directly linkedito only one carbon atom), a secondary carbon atom (die rectly linked to two atoms of carbon), out even may ibe a tertiary carbon atom (directlyrlinkedto three atoms of carbon), although .it is in general preferred. tofemploy thezprimary allyl-type .hy drocarbon. halides. Aliphatic primary allyl-type hydrocarbon halides are particularly preferred; nllyl type hydrocarbon halides which have been reacted with epoxid-e compounds ace ordin'g' to .athe' process of the. invention have contained onlythe one. atom of halogen. Allyl-type hydrocarbon halides containing more than. the. one. atom;.of halogenalso have been successfully empl-oyedin theprocess of the invention. If more. than one' atom of halogen isrpresent in the allyl type halide, the additional atomor atoms maybe in the allyl position relative to an olefinic bond, or prererably it or they may be in a position or positions otherthan the .allyl position relative-to an olefinic bond, e. g., in vinyl position. Representative allyl-t'ype halides; as hereinbef ore and. hereinafter defined, which may be employed in the process of the invention. include among othcrs the following: aliphatic allyI-type hydrocarbon primary monohalides, such as allyl chloride, allyl bromide; methallyl chloride, methallyl bromide,

crotyl chloride, crotyl'bromide, 2-ethyl-3-chlorol-propene, 2 ethyI-S- br-omo-l-propene, '2-isopropyl-3-chloro-1-propene, 2n-propy1-*3-bromo-1- propene, l-cliloro-Zmentene, 1-bromo-3-methyl- Z-pentene, 1-chloro-2-ethyl-#2-butene; l-bromo- 2-ethy1-2-butene, 1-chloro-2 butyl-Z-butene, 1- bromo2--isobutyl2ebutene, l-chloro-2 pentyl-2- pent'en'e, 1 chloro 2 butyl 3 methyl 2 -butene, 1-bromo-2emethyl 2 octene, 3-chloro-2- neopentyll propene, 3-bromo--2--hexyl-1-propone, 1-chloro-2-ethyl-8 -methyl--2-butene, 1- bIOmO'Q-BthYI 3 methyl-2-butene, lechloro-z tetradecene. and l-chloro-2 hexyl-2-pentene; aliphatic allyl-type hydrocarbon sec-ondarymonohalides, suchas .SechIoro-I-butene, 'B-bromo-I butene, 3-chloro-l-penteue, 3-bromo-1-pentene; S-chloro-l-hexene; 4--chl oro-2-hexene, 4-chloro- 5-methyl-2-whexene, and 5 chloro 3 heptene". Still. other allyl-typehydrocarbon halides which may be reacted according to the processof the invention with organic epoxide compounds in"- cludes the following: 3-chloro-1-cycloh-exene; '3- bromo-l-cyclohexene, IA-dichloro-Z-butene, 1,4 dibro-mo-Z-pentene, cinnamyl chloride, cinn-amyl bromide, 3-chloro2-phenyl-l-propene, B-bromo 2-phenyl-l-propene, 1-chloro 2,4-pentadiene, a1"- lylidene chloride, and -5-methyl 3- chlorocyclo hexene; I

While. the generic invention applies broadly to use in the process of any allyl-type hydrocarbon halide,.a preferred embodiment of the invention is limited to thealiphat'ic beta-methylenehydro carbon primary monohalides, such as a'll-yl chloride, allyl bromide, methallyl chloride methallyl'. bromide, 3-chloro-Z-ethyl-l-propne, .3.-bromo-2.-isopropyl-l-prooene and homologs and-- analogs. thereof. This preferred 1 group, which is distinguished onthe one hand by'athe great reactivity of the olefiniebond; the tendency of the members to polymerize, and on the other hand by the desirable properties of the products obtained therefrom according to the invention, may be described by means of the formula inwhich X is an atom of halogen, i. e., bromine or chlorine, and R is a hydrogen atom or a monovalent aliphatic hydrocarbon group, such as an alkyl group.

The process of the present invention may be carried out by heating at a suitable elevated temperature and for a suitable time a mixture of. the selected reactants and after the desired reaction has proceeded to a substantial extent recovering from the resulting mixture the product formed by the reaction. Since the reaction occurs in liquid phase, the reaction mixture should be kept partially or Wholly in liquid phase during the heating operation. The temperature that is employed will depend toa limited extent upon the particular reactants involved as well as upon the other reaction conditions, e. g., time, proportions of reactants, etc. It has been found that, if the temperature is too low, the desired reaction does not occur, while at excessively high temperatures polymerization, decomposition, and/or undesired side reactions predominate and inadequate yields of the desired product are obtained. The lowest temperature generally suitable is about 100 C., and temperatures of at least 130 C. are preferred. While in some instances temperatures as high as 350 C. may be employed, preferred temperatures, because of the optimum yields of the desired products resulting therefrom, are below 250 C.

The allyl-type hydrocarbon halide and the epoxide compound preferably are employed in amounts corresponding to approximately equimolar proportions of the two reactants. It has been discovered that a moderate excess of the epoxide compound relative to the allyl-type hydrocarbon halide has a beneficial effect upon the rate of reaction and therefore favors higher conversions to product other conditions being equal. Generally speaking, amounts of the two reactants corresponding to mole ratios of olefinic halide: epoxide compound from about 10:1 to aboutlzlO may be used, a preferred range, because of the optimum conversions to desired product and the more efficient operations provided,

being mole ratios from about 2:1 to about 1:2. Although the presence of an inert solvent ordinarily will not be required, suitable inert solvents may be included in the reaction mixture, as when one of the reactants is a gas, or a solid at the reaction temperature, and it would be convenient to handle suchreactan-t in the form of a. solution rather thanin the pure state.

- The reaction proceeds in the absence of added catalysts, although higher reaction rates and hence shorter reaction periods may be obtained by conducting the process in the presence of a suitable catalyst for the reaction. Because of the polymerizable character of the organic compounds involved in the process, the catalyst should be one that does not tend to cause excessive polymerization of reactants and/or product but which nevertheless favors the desired reaction without favoring undesired side reactions. Small amounts of copper, or of copper compounds, especially cuprous salts, when contacted with the reaction mixture, increase the reaction rate markedly. Surprisingly, they do so without noticeably favoring formation of polymers; hence 8 higher conversions to the desired products may be obtained, other conditions being equal, by conducting theprocess in the presence of copper or a copper salt than in the absence of catalysts.

Among the copper compounds which may be employed are the halides of copper, including the bromides, the chlorides, and the iodide, copper sulfate,.copper nitrate, copper borate, azurite, cuprous carbonate, etc., as well as organic salts of copper, e. g., copperiacetate, copper naphthenate, copper zenzoate, copper palmitate, copper salicylate, etc., and complexes of copper, e. g.,

ture intimately contacted, while heating, with the supported catalyst. When a copper salt, such as a copper halide, is employed as the catalyst, the amount of the catalyst conveniently may be in excess, that is, an amount such that solid'catalyst is present during the reaction. Amounts of the catalyst from about 0.05 to about 50%, preferably from about 0.5 to about 10%, by weight of the reactants may be used. More or less may be employed if desirable.

An especially effective catalyst has been found to be the solid material remaining as a residue from a cycle of the process conducted in the presence of an excess of a solidcopper salt. This W111 be illustrated in one of the examples Thus, in an original cycle the mixture may be heated in contact with copper metal. A part of the copper reacts forming a solid residue. Or a copper salt as such, for example, a copper halide, may be employed as the catalyst. At the conclusion of the heating, the solid remaining is allowed to settle out, and the liquid is removed for recovery of the reaction product. The solid residue remaining, when employed as the catalyst in a succeeding cycle, carried out by adding fresh reactants thereto and heating as aforesaid, is more active weight for weight than a copper salt that has not been employed previously in the process of the invention.

The process of the invention may be conducted in any suitable manner and in any type of equipment familiar to those skilled in the art and suitable for processes of the manipulative character here involved. However, since the reaction mixtures are corrosive to certain metals, the equipment should be constructed of or lined with a suitable corrosion resistant material. Glass, porcelain; nickel, gold, tantalum, molybdenum, iridium, palladium, chromium, platinum, cadmium, or suitable alloys thereof; rubber, synthetic organic chemically-resistant surface coatings, and the like, are included among suitable materials of which at least the surface of the equipment exposed to contact with the reaction mixture may be constructed or lined. Certain ferrous materials of construction are less desirable. Thus, it has been found that the presence of iron, as in pure state or as in the various carbon steels, in contact with thereaction mixture under the reaction conditions of the process favors the formation of polymers and tars apparently derived from the allyl-type hydrocarbon halide and surprisingly, conversion of the epoxide compound, for example in the case of epichlorohydrin, to glycerol dichlorohydrin. It has been attics that-tilematures accent? use tldyed iii theexecutioiif or the pi cess er; the in- I vention.""-Suitab1e stainless steels include, for

example, nickel-chromiumsteels such as AISlC Types Nos. 304, 316, 309; 311-, 301, and 325 (see lVlet a1s and Alloys Data Book, by L. Hoyt,

Rf nhdldPi1b1ishirig' cemeteries; York, a

process may" be" carried them a eat-unwise; ttnt, or onsensus manner. A suitable batoliwisefprocedurfeis t6 prepare amixture oi th ct'antsfwhich may or may not have been ed, and weed the catalys'tif oneis to be' em loyed. The'mixture may be heatedin' asuit V "resistant vessel; such as one equippe wit condensing means; suchas are? flux condiisenin the case of reactants boilin at or near the reactiofi temperature; or in a closed autoclave in the case of reactants which boil at temperatures below the reaction temperatures to be employed. With reactants which are immiscible with each other and/or with the catalyst, it has been found to be desirable to 4 agitate thereactionmixture during the heating by means of a suitable' agitating device to provide intimate contactbetween the; reactants or the reactants and the catalyst. The course of the reaction may be followed by withdrawing sample's-yfroznthe reaction mixture and subjecting them :to analysis. In continuous operations; streams of the reactants; which; may have been preheated, may be mixed and the mixture held at the desired temperature; for a suitable time The catalyst, if one isemployed, may be added to either or' both of the reactants priorto their admixture; or itmay be added to; the mixture of reactants- Also, the catalyst, for example, a supported catalyst; maybepositioned in a reac- .tior-r zone and'the reaction mixture passed into contact therewith under suitable conditionsof temperature and time. The pressure upon the reaction mixture maybe either at, below, or above the atmospheric pressure, subject to therequirement for maintaining the mixture in liquid phase. If superatmospheric pressures are employedthey may be;autogenous, as developed upon he'ating of the reaction'mixture in aclosed vessel, ior'ithey'may be applied, as by the application of mechanical pressure or an inertgasie. ga, argon,'nitrogen, methane, helium, etc under pressure; to the reaction mixture. M After the reaction has proceeded to the desired extent the product may be recoveredfrom the reaction mixture-by any suitable procedure. 'I-he catalyst; if a solid suspended in or dispersed throughout themixture may be removed yfi ticm: sedimentation, centrif ug-ation or HR? opera-- tions-tand-may' be employed, with the advantage hereinbefore pointed cut in a further cycle of the process. The "desired product may be re covered from the reaction mixtureby fractional distillatiom by treatment with selective solvents-,-

by crystallization, or other applicable methods-v fractional pdistillation generally being preferred: Un-re'actedi allyl-type hydrocarbon and/or epoxide e mpound -may berecovered and recycled in whole or in p'artlthrough the process.

The following xan'ipls are given" not 111m ages theredff 84 grams (1.1 mole) of allyl chloride. their: x ture there was suspended .5 grams of copper foil 0.002 inch 45 millimeters mercury pressure was 001- lc'cted separately and found to be allyl bis(ch10romethyl'l'carbinyl' ether, having the structure cm oa cm o -on Hr-Cl 1 to the ally-1" bis)(cl'iloromethylJ-carbinyI ether was 629% based on the epichlorohydrin anda5'l.'r% based on the allylchloride. -The yield of allyl bis(chloromethy1) carbifiyfther was 70.5% based on theebiehiorch aee corisiirriflda arid- 90.0% based-oh theauyicmoeaeceasumea 1 remier: I This example" illustrates a cyclic" process utilii-i' ing a catalyst previously used for effecting the reaction between an allyl ty'pe. hydrocarbonhalide and an epoxide compound; Aswthe ca-ta; lyst; there w-as' employed the moist solid res'idiie or sludge remaining in the 'g'lassvesseliafter the" i the'previousexample, a furtheri'experimeiit was conducted in the manner employed 'iir'lilx ample I, but at a reaction temperature of 165 C. to 1J2? C; ILhe ally'rl bis(chloromethy1)carbiny1 ether was recovered in a conversion of 27% based uponftlie and ft of epichlorohydrin consumed, demonstratingthe marked superiority of the cat-. alyst employed in the first experiment described under thisexample. i If.

EdIdM'iQZe'III 1a 1 gasses-1* ailments, tees 552 grams (5.97 moles) of epichlorohydrin and 502 grams (6.56 moles) of allyl chloride. A piece of .copperfo'il 0.002 inch thick and 34 square inches in area was added. The autoclave was closed and heated at 147 C. to 166 C. for 66 hours. Upon fractional distillation of the resulting mixture, allyl bis(chloromethyl)carbinyl ether. .was recoveredin conversions of 70% and 63.6%, respectively, based upon the amount of epichlorohydrin and allyl chloride employed, and in yields of 77.5% and 82.6%, respectively, based upon the amount of epichlorohydrin and allyl chloride consumed.

Example IV Yield, percent on Reactant Consumed Conversion,

percent on Reactant Employed Ally] chloride 90 Epichlorohydrim'. 65. 7

Example V In the absence of added catalyst, and in a glasslined autoclave, allyl chloride and epichlorohydrin present in 1.1:1 mole ratio reacted in 15 hours at 164 C. to 170 C. to form allyl bis(chloromethyl) carbinyl ether in conversions of 6.5% and 5.8 respectively, based upon the epichlorohydrin and the allyl chloride employed. As in the previous experiments, polymer formation was negligible.

Example VI A mixture of 103 grams epichlorohydrin, 97 grams allyl chloride and 28 grams of cuprous chloride was heated in a nickel autoclave for 25 hours at 162 C. to 166 C. The autoclave then was cooled, the contents withdrawn and the liqquid, after separation from the catalyst, distilled. Conversion of allyl chloride employed to allyl bis(chlormethyDcarbinyl ether was found to be 47.5% and conversion of epichlorohydrin to product was found to be 54.4

Example VII Yield, percent on Reactant Consumed Conversion, percent on Reactant Employed Allyl chloride.

Epichlorohydrin As a demonstration of the desirability of providing intimate contact between the solid catalyst and the'liquid reaction mixture, when the foregoing experiment was repeated without agitation of the' reaction mixture during the heating period, the conversion to allyl bis(chloromethyl) carbinyl ether 'wasabout 8% based on the epichlorohydrin employed. The results thu obtained suggest that the mechanism of the catalysis is in large measure one of heterogeneous catalysis rather than homogeneous catalysis by copper compounds dissolved in the liquid mixture.

Example VIII In a glass reactionvessel similar to the one employed in Example I there were mixed 64 grams (1.1 mole) of propylene oxide, 92 grams (1.2 mole) of allyl chloride, and 2 grams of cuprous chloride. The mixture was heated in th closed vessel at C. to 169 C. for 15 hours. The cooled liquid then was decanted from the residual solids in the vessel'and' fractionally distilled. The product.

which was found to have a boiling point of 64- 65 C. under a pressure of 50 millimeters of mercury, was 7 identified as allyl 1-chloro-2-propyl ether having the formula The product was recovered in a conversion of 71 based on the propylene oxide employed and 66% based on the allyl chloride employed.

Example IX In a similar manner, allyl chloride and glycidyl ally1 ether were caused to react to produce the diallyl ether of glycerol alphamonochlorohydrin. By heating in a closed glass vessel at 165 C. for 15 hours a mixture of 91 grams (0.8 mole) of allyl chloride, 68 grams (0.89 mole) of glycidyl allyl ether and 2 grams of cuprous chloride, and fractionally distilling the resulting mixture there was obtained in 87% yield on the allyl chloride consumed and in 65% conversion on the glycidyl allyl ether employed the indicated product distilling at from 126.5 to 1285 C. under a pressure of 50 millimeters of mercury. The product was found to have a refractive index (12 of 1.4570 and a specific gravity (ch 9) of 1.0357.

Example X This example illustrates the reaction of an allyl-type hydrocarbon halide containing two halogen atoms, one being in the allyl position with respect to the olefinic bond and the other in the vinyl position, with an epoxide compound In a glass vessel similar to the one employed in Example I there were mixed 111 grams (1.0 mole) of 1,3-dichloropropene, 83 grams" (0.9 mole) of epichlorohydrin, and 2 grams of cuprous chloride. By heating the mixture in the closed vessel at 165 C. to C. for. 15 hours and fractionally distillingthe liquid mixture produced, 3-chloroallyl bis(chloromethyl)- carbinyl ether was obtained in a 31% conversion of epichlorohydrin to product and a 27.5% conversion of 1,3-dichloropropene to product. The

' millimeters mercury pressure and was found to yllcarbinyl ether and allyl decyl-bis(chloromethyDcarbinyl ether.

Another subgroup of compounds which are of especial interest, because of V the distinctive branched-chain structure of the hydrocarbon radical directly linked to the ether oxygen atom, comprises those ethers represented by the immediately preceding structural formula when R* is the hydrocarbon radical of a beta-methylene beta,gamma-olefinic aliphatic primary alcohol containing a tertiary olefinic carbon atom in the beta-position. This group may be represented by the formula in' which R represents the hydrogen atom or an alkyl group and X representschlorine or bromine, and Rf is an alkyl group, such as an alkyl group containing from one to ten carbon atoms. Illustrative compounds within this preferred subgroup which may be prepared according to the process of the invention include among others the following: methallyl bis(chloromethyl)carbinyl ether, methallyl bis(bromomethyl)- carbinyl ether, methallyl methyl-bis(chloromethyDcarbinyl ether, 2-ethyl-2-propenyl bis- (chloromethyDcarbinyl ether, 2-ethy1-2-propenyl butyl bis (chloromethy1)carbinyl ether, methallyl pentylchloromethylbromomethylcarbinyl ether, 2-butyl-2-propenyl octyl-bis(chloromethyDcarbinyl ether, 2-neopentyl-2-propenyl decyl-bis(chloromethyl)carbinyl ether, 2-octyl- 2- propenyl t butyl bis(bromomethyl) carbinyl ether, methallyl 1,3-dimethylbutyl-bis(chloromethyDcarbinyl ether, as well as their various homologs and analogs having structures defined by th formula. p

The compounds illustrated above possess properties which distinguish them from heretofore known compounds and which render them of improved value for various applications. The presence of two halomethyl groups (in which each halogen is linked to a primary carbon atom) substituted on the carbon atom that is directly linked to the ether oxygen atom imparts desirable properties to the compounds not found in ethers of halogen-substituted carbinols in which there is present only one halogen atom,

' or, if two halogen atoms are present, one is linked to a primary carbon atom and another is linked to a secondary or a tertiary carbon atom. The presence of the beta,gammaolefinic bond. in the hydrocarbon radical linked to the ether oxygen atom also contributes unique properties to the novel compounds, which properties are not found in ethers of halogen-substituted carbinols formed by substituting for the hydroxyl hydrogen atom of said carbinols, for example, an alkyl group, an aryl group, or a cycloalkyl group. 7 p

The compounds obtainable by the process of the invention possess wide utility. They are valuable as versatile chemical intermediates. For. example, the halogen atoms may be replaced by hydroxyl as by hydrolysis, and valuable allyltype monethers oi trihydric alcohols, e. g., of glycerol, may be prepared. Allyl-type betaethers of glycerol thus obtainable may be employed for the preparation of improved alkyd resins according to the invention disclosed and claimed in U. .S. Patent to Theodore W. Evans and David E. ,Adelson, No. 2,448,258, August. 31, 1948. ,Such glycerol'ethers may also be polyelevated temperature as disclosed and claimed'in the pending application of Hans Dannenberg and David E. Adelson, Serial No. 4'70, filed January 3, 1948, now U. S. Patent No. 2,545,689, or suitable glycerol ethers thus prepared may be reacted with monobasic carboxylic acids to obtain valuable polymerizable esters. The ethers of beta,- gamma-olefinic alcohols with bis(halomethyl) carbinols, particularly the ethers of 2-methylene aliphatic primary alcohols with saturated aliphatic bis(chloromethyl) substituted" carbinols, Y are also useful as intermediates'for the preparation of sulfur-containing high molecular weight prod ucts by condensation with water-soluble sulfides and polysulfides, such as alkali ,metal'sulfides and polysulfides, and ammonium or alkaline earth metal sulfides and polysulfides. Ethylenic polymers of the novel ethers of the invention may also be prepared by application of known methods for the polymerization of polymerizable vinyl compounds. Products obtainable by the process of the present invention also are of interest and may be used as biologically active compounds and as precoursers of biologically active compounds,

and in a wide variety of other applications.

We claim as our invention:

1. Allyl bis(chloromethyl)carbinyl' ether; I

2. Methallyl I bis(chloromethyl) carbinyl ether.

3. 3 Chloroallyl bis(chloromethyl)carbinyl ether.

4. An ether wherein one radical linked to the ether oxygen atom is a hydrocarbon radical of ,a beta-methylene aliphatic primary alcohol and the other radical linked to the ether oxygen atom is the di-chloro substituted hydrocarbon radical of an aliphatic bis(chloromethyl) carbinol.

5. An ether of a beta,gannna-olefinic alcohol with a carbinol having two halomethyl groups directly linked to the carbon atom of the carbinyl group.

6. A process which comprises heating a mixture of about equimolaramounts of allyl chloride and epichlorhydrin in contact with copper at about 180 C. to 185 C. for about 15l10urs,.and recovering the allyl ether of bis(chloromethyl) ca-rbinol from the resulting mixture.

7. A process which consists in reacting a beta,- gainma-olefinic hydrocarbon halide with an epoxide compound at a temperature within the range of from about C. to about 350 C. to produce an ether of a betagammawlefinic a1- cohol with a halornethyl-substituted carbinol.

8. A process which consists in reacting allyl chloride with epichlorohydrin at a temperature Within the ran e of from about 100? C..to about 350 C. to produce allyl bis ch1oromethyl)carbinyl ether.

9. A process which consists in reacting in liquid phase a Z-methylene primary aliphatic hydrocarbon halide with a glycerol epihalohydrin in the presence of a copper salt to produce an ether of a bis(halemethyl) carbinol with a beta-methylene primary aliphatic alcohol.

10. A cyclic process for the preparation of allyl bis(chlor0methyl) carbinyl ether which com.- prises heating in liquid state a mixture of allyl chloride and epichlorohydrin present in mole ratios from about 10:1 to about 1:10 at about C. to about 250 C. in contact with an excess of a copper salt whereby there is produced an amount of said allyl bis(chlorom-ethyl) carbinyl ether, substantially separating the liquid mixture containing said ether from the remaining excess of said copper salt, and contacting a fresh mix- 17 ture of allyl chloride and epichlorohydri'n with the remaining excess of said copper salt and heating the mixture in liquid phase while in contact with the remaining excess of said copper salt at about 130 C. to about 250 C. to produce a 5 further quantity of the allyl bis(chlorometh'y1)- carbinyl ether. "7

11. A process which comprises heating allyl chloride and epichlorohydrin together in the presence of a cupreous catalyst at a temperature within the range of from about 100 C. to about 350 C. and recovering alyl bis(chloromethy1)- carbinyl ether from the resulting mixture.

12. A process which comprises heating a beta,-

ga-mma-olefinic hydrocarbon halide and a 15 glycerol epihalohydrin together in the presence of a cupreous catalyst at a temperature within the range of from'abo-ut 100 C. to about 350 C. and recovering an ether of a bis(halomethy1) REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,236,919 Raynhart Apr. 1, 1941 2,241,421 Price May 13, 1941 2,363,614 Patrick Nov. 28, 1944 2,437,866 Vance et a1 Mar. 16, 1948 2,462,602 Botteron Feb; 22, 1949 2,464,747 Grosser Mar. 15, 1949 2,541,091 Oroshnik Feb. 13, 1951 

5. AN ETHER OF A BETA,GAMMA-OLEFINIC ALCOHOL WITH A CARBINOL HAVING TWO HALOMETHYL GROUPS DIRECTLY LINKED TO THE CARBON ATOM OF THE CARBINYL GROUP.
 7. A PROCESS WHICH CONSISTS IN REACTING A BETA,GAMMA-OLEFINIC HYDROCARBON HALIDE WITH AN EPOXIDE COMPOUND AT A TEMPERATURE WITHIN THE RANGE OF FROM ABOUT 100* C. TO ABOUT 350* C. TO PRODUCE AN ETHER OF A BETA,GAMMA-OLEFINIC ALCOHOL WITH A HALOMETHYL-SUBSTITUTED CARBINOL. 